Articles having thermoset coatings and coating methods

ABSTRACT

A method to prevent corrosion of a susceptible article of a two-article system, in which first and second articles of the two-article system have surfaces facing one another and in which the two articles have different anodic indices includes applying a coating material to the surface of the first article and curing the coating material on the surface of the first article. The method further includes contacting and securing the surface of the first article with the surface of the second article. The two articles exhibit substantially no corrosion following exposure to a corrosive environment under standard GMW17026 for a 15 year simulated test.

CROSS-REFERENCE TO RELATED APPLICATION DATA

This application claims the benefit of and priority to Provisional U.S.Patent Application Ser. No. 62/111,495, filed Feb. 3, 2015 andProvisional U.S. Patent Application Ser. No. 62/257,015, filed Nov. 18,2015, the disclosures of which are incorporated herein in theirentirety.

BACKGROUND

Certain aspects of this disclosure relate to articles and/or assemblieshaving coated components or features, and processes for coating sucharticles. In particular, certain aspects of the disclosure relate to ametal article at least partially covered with one or more thermosetcoatings and/or an inorganic coating capable of preventing galvaniccorrosion from occurring when the article is in contact with adissimilar metal or other material in the presence of an electrolyte,assemblies having such an article, and processes for producing sucharticles.

There are many different types of corrosion. In general, corrosion isthe conversion of a material, for example, a metal, to a more stableform. There are, however, two major types of corrosion: general oruniform attack corrosion; and galvanic corrosion. General or uniformattack corrosion can occur, for example, when iron is in a wet or dampenvironment and it corrodes, forming iron oxide in the process.

Galvanic corrosion, on the other hand, occurs when two materials havingdifferent anodic indices or electro-potentials are in contact with, orclose proximity to, one another in the presence of an electrolyte. Theelectro-potential difference produces electron flow between thematerials. In such a system, one of the materials is more active (orless noble) and serves as an anode and the other material is less active(or more noble) and serves as a cathode. The anode corrodes at anaccelerated rate, while the cathode corrodes at a lesser rate.

An example of a system in which galvanic corrosion can occur is a steelbolt securing a magnesium panel to an object in the presence ofnon-distilled water, such as a salt spray environment. The magnesium,being less noble than the steel, will corrode at an accelerated rate,while the steel will corrode at a slower rate. This problem is notlimited to dissimilar metals, in that galvanic corrosion can occur when,for example, a steel bolt is used to secure a non-metal panel, such as acarbon fiber panel. In this system, the steel being less noble than thecarbon fiber will corrode at an accelerated rate, while the carbon fiberpanel will corrode at a slower rate. Again, when two materials havingdifferent anodic indices are in contact with or close proximity to oneanother, the potential for galvanic corrosion is present with the lessnoble material exhibiting accelerated corrosion.

Once an electrolyte is present, for example by the presence ofnon-distilled water, such as salt spray and the like, corrosion canoccur, which can weaken the structural integrity of whatever material isacting as the anode by virtue of its relative electro-potential and/orresult in an undesirable aesthetic appearance. Galvanic corrosion is aproblem in the automotive and aerospace fields, amongst others.

In, for example, the automotive industry, there is a strong desire toreduce the weight of vehicles. Such light-weighting, is driven by theeffort to increase fuel efficiency. As such, lighter weight materials,such as aluminum, magnesium and carbon fiber, are used in body and drivetrain components. However, in many instances, the use of light-weightcomponents cannot be carried over to fasteners, such as bolts and thelike. Thus, the bolts used are typically iron alloy materials, such assteel. The reluctance to use these light-weight materials in fastenersis due to their increased cost and the acceptance of steel fasteners,their strength and overall mechanical properties.

To prevent galvanic corrosion, similar materials or different materialswith similar electro-potentials (anodic indices) can be used. However,this limits the types of combinations of materials available for thedesired application.

In another scenario, a barrier can be imposed between the dissimilarmaterials. For example, a bolt coated with a polymeric material such asnylon or a polymeric seal can be disposed between the head of a bolt andthe panel. However, nylon coatings or seals may not discourage galvaniccorrosion, and may not meet the general mechanical requirements of thesystem. For example, the coating may be too thick and interfere with theengagement of the bolt with a female member (e.g., a nut), or increasethe coefficient of friction when driving the bolt, or the resiliency ofthe coating or seal may result in the loss of tension when subject totemperature changes, e.g., heat up and cool down, of the system. Inaddition, such polymeric coatings or seals may not provide the barrierneeded to prevent electron transfer between the dissimilar materials.Furthermore, resilient polymeric material may not maintain structuralintegrity with temperature fluctuations, vibrations and other forces towhich the system may be subjected.

Accordingly, there is a need for a method for preventing galvaniccorrosion in systems that have dissimilar materials in contact with orin close proximity to one another in the presence of an electrolyte.Desirably, such a method uses materials that withstand heat up and cooldown cycles of the system while maintaining protection of the materialsfrom galvanic corrosion. More desirably still, such a method usesmaterials that maintain the mechanical properties and requirements ofthe system. Still more desirably, such a method can be carried out in amanufacturing environment, in a cost effective manner.

There is also a need for a multi-part article system that exhibitsresistance to galvanic corrosion under a variety of adverseenvironmental conditions, while maintaining the required mechanicalproperties, conditions, characteristics and specifications of thesystem.

SUMMARY

In accordance with one exemplary aspect, an article of a first material,such as a metal article comprising at least a first surface isdisclosed, the first surface being at least partially covered by athermoset coating. In some examples the article is entirely covered bythe thermoset coating. In various examples, the thermoset coating is arapid-cure thermoset coating. In certain embodiments, the rapid-curethermoset coating material cures in about one minute or less when thecoating material in contact with the metal article and is exposed to aninduction heater. In other examples the coating material cures inapproximately thirty seconds or less. In some embodiments, the coatingcures in either of the above time periods (or others) when exposed totemperatures between about 350 degrees to 475 degrees Fahrenheit. Incertain examples, the thermoset coating is a cross-linked epoxy coating,and may be a fusion-bond epoxy coating.

In some embodiments, the thermoset coating is made from a powder, suchas an epoxy powder, that is subsequently cured to form the thermosetcoating. In various examples, the coating is made from a powdercomprising an epoxy resin and one or more curing agents or hardeners.The curing agents or hardeners may consist of or comprise one or moreamines, anhydrides, acids, phenols and/or alcohols. In certain examples,the thermoset coating is made from a fusion bonded epoxy coating, suchas 3M® Fusion Bonded Epoxy 413, 3M® Scotchkote 426 FAST and/or AxaltaAlesta 74550. In some examples, the coating material cures inapproximately thirty seconds or less when subjected to a temperature ofabout 400 to 450 degrees Fahrenheit, while in others about 420 to 430degrees Fahrenheit, while in still others about 425 degrees Fahrenheit,after being applied as a powder to the article.

In various embodiments, the article further comprises a lubricantcoating in contact with at least a portion of the article. In someexamples, the lubricant coating covers or is in contact with at least aportion of the thermoset coating, while in others it covers the entirearticle and/or the entire surface of the thermoset coating. In someembodiments, the lubricant coating consists of or comprises one or morewaxes, for example a polyethylene wax, molybdenum disulfide, or one ormore fluoropolymers.

In some examples, the thermoset coating has a substantially uniformthickness. In various embodiments, the coating thickness (regardless ofthe geometry and/or shape of the article) only deviates from about 0.002inches or less from the overall average coating thickness, while inothers about 0.001 inches or less, and in still others about 0.0005inches or less. In certain embodiments, the thermoset coating thicknessis about 0.005 inches or less, while in others it is approximately0.0035 inches or less, or approximately 0.0025 inches or less, orapproximately 0.0015 inches or less, or approximately 0.0010 includes orless, or approximately 0.0005 inches or less. In various embodiments,the thickness is between approximately 0.0005 to 0.005 inches,approximately 0.0015 to 0.0035 inches, and approximately 0.0025 inches.

In certain examples, the article comprises an inorganic coating,including but not limited to a ceramic coating. In some examples thearticle is electroplated and/or plasma-treated, for example the articlemay comprise a Keronite® coating. These examples may also comprise oneor more of the thermoset coatings described herein and/or one or morelubricant coatings on top of the inorganic, e.g. ceramic, coating (i.e.,article→ceramic coating→thermoset coating→lubricant→).

In certain examples, the thermoset coated article has a heat resistancesuch that it may be exposed to elevated temperatures for extended timeperiods without adverse effects to the coating. For example, in certainembodiments the coated article is capable of withstanding approximately350 degrees Fahrenheit for approximately thirty minutes without adverseeffects to the coating, such as softening, melting, flowing, dripping,charring and the like.

In some embodiments, the article is a fastener, for example a fastener,bolt, clip or shank. The article may consist of or comprises any metalor metallic alloy. In certain embodiments, the article is iron or aniron alloy, such as steel. In others, such as the articles that alsocomprise a ceramic coating, the article is magnesium, aluminum,titanium, or alloys thereof.

In certain examples, the thermoset coating comprises a first thermosetcoating, and a second thermoset coating is applied to the article on topof the first thermoset coating, a portion thereof, or the entire surfaceof the article, including any or all portions already covered by thefirst thermoset coating. In various examples, the first thermosetcoating is a rapid-cure thermoset coating and the second thermosetcoating is not a rapid-cure thermoset coating. For example, in someembodiments the first thermoset coating cures in about one minute orless when exposed to an induction heater while in contact with the metalarticle, while the second thermoset coating requires a longer cure timeat an equivalent temperature range used for curing the first thermosetcoating, for example ten minutes or more, or fifteen minutes or more.

In some examples, the second thermoset coating comprises one or moreepoxies, polyesters or polyurethanes, while in others the second coatingcomprises an epoxy/polyester mixture. In one example, the secondthermoset coating is made from a Valspar® TGIC polyester (such asPRA60001). In various examples, the second thermoset coating isonly-partially cross-linked, for example when it is exposed to heat fora period of time shorter than necessary to achieve full curing. Theseexamples comprising a second thermoset coating may also comprise thelubricant coating, for example, where the lubricant coating covers atleast a portion of the top surface of the second thermoset coating.(i.e., article→first thermoset coating→second thermosetcoating→lubricant).

In accordance with another aspect, an assembly is disclosed, theassembly comprising a first article and a second article configured tobe fastened or connected to the first article, wherein the two articleshave dissimilar electro-potentials such that galvanic corrosion mayoccur when the articles are in the presence of an electrolyte. The firstarticle may be partially or entirely coated with one or more thermosetcoatings, such as any of the coatings described above or elsewhere inthis disclosure, and optionally may be coated with a lubricant coatingpartially or entirely on the top surface of a thermoset coating. Incertain examples, the second article comprises, is connected to, or isconfigured to be connected to a third article. In various embodiments,the second article is also partially or entirely covered with one ormore thermoset coatings, and optionally may be coated with a lubricantcoating partially or entirely on the top surface of a thermoset coating.In certain examples, the second article may also comprise anon-thermoset coating, such as a thermoplastic coating.

In accordance with another aspect a process is disclosed. In someexamples, the process comprises applying a powder coating to an article(for example by spraying the powder coating onto the article optionallyafter the powder coating and/or article has been subjected to a processthat creates a charge on the surface of the powder coating and/orarticle such as a tribo charge). The process may also comprisetransporting the powdered article to a heat source, such as an inductionheater. In certain examples, a metal article is at room temperature orambient temperature, the powder is applied to the metal articleoptionally after the powder coating and/or article has been subjected toa process that creates a charge on the surface of the powder coatingand/or article such as a tribo charge, and then the article and powderare heated, for example by exposure to an induction heater, such thatthe powder cures into a cross-linked thermoset coating. The process mayfurther comprise transporting the coated article to a lubricatingstation, where one or more lubricants (e.g. a polyethylene wax emulsion)are applied to the article, for example through spraying.

The process may also comprise drying the lubricated article, for examplethrough another application of induction heating. In some examples,prior to lubrication another thermoset coating material is applied andat least partially cured on the article. In certain examples, theprocess may comprise forming a ceramic coating on the article, and thenapplying one or more thermoset coatings (for example, a rapid-cure thena non-rapid cure thermoset coating) and then optionally applying one ormore lubricant coatings.

Also disclosed are methods to inhibit and/or prevent corrosion, such asgalvanic corrosion of a susceptible article of a two-article system, inwhich first and second articles of the two-article system have surfacesfacing one another and in which the two articles are comprised ofmaterials having different anodic indices, the method including applyinga coating material to the surface of the first article, curing thecoating material on the surface of the first article and contacting andsecuring the surface of the first article with the surface of the secondarticle, such that the two articles exhibit substantially no galvaniccorrosion following exposure to a corrosive environment under standardGeneral Motors Worldwide Engineering Standards test procedure GMW17026,“Accelerated Corrosion Laboratory Test for Galvanic CorrosionMechanisms” for a 15 year simulated exposure test. In an embodiment ofthe method, when the cured coating material is present on at least ahead of a steel bolt mounted to a magnesium coupon, the magnesium couponexhibits less than about 20%, 10%, 5%, 3%, or 1% of pitting as comparedto an uncoated steel bolt mounted on the magnesium coupon corrosionfollowing exposure to a corrosive environment under standard GMW17026for a 15 year simulated test.

In an embodiment of the method to inhibit and/or prevent corrosion suchas galvanic corrosion, the coating material is a thermoset material. Thethermoset material can be an epoxy material that cross links duringcuring to form a cross-linked epoxy coating. One such epoxy material isa fusion bond epoxy material. The epoxy material can further comprise acuring agent or hardener, such as one or more of more amines,anhydrides, acids, phenols, alcohols and thiols. The epoxy material canfurther comprise one or more of a filler and a pigment. In a method, theepoxy material cures in approximately thirty seconds or less whensubjected to a temperature of about 400 to 450 degrees Fahrenheit toform the cross-linked epoxy coating.

The method can include applying the coating material as a powder. Thepowder can be sprayed onto the article, for example, after a charge hasbeen applied to the powder and/or the article.

In one method, the coating material comprises a first coating materialand a second coating material, such that the first coating material isfully cured to form a first cured layer and the second coating materialis applied onto the first cured layer. The second coating material canbe a thermoset material. The first coating material can be a fast curingmaterial and the second coating material can cure at a slower rate thanthe first coating material.

In a method, the curing is heat curing. The heat curing can be inductionheat curing and can include subjecting the article to a magnetic fieldafter the thermoset material has been applied to at least a portion ofthe surface of the article.

In an embodiment of the method, the second coating material is alubricant. The lubricant can be one or more of a polyethylene wax, aparaffin wax, a carnauba wax, and a solid lubricant. The solid lubricantcan be one or more of molybdenum disulfide and a fluoropolymer.

In an embodiment of the method, the coating material, when cured, has asubstantially uniform thickness of about 0.005 inches or less, while inothers it is approximately 0.0035 inches or less, or approximately0.0025 inches or less, or approximately 0.0015 inches or less, orapproximately 0.0010 includes or less, or approximately 0.0005 inches orless. In various embodiments, the thickness is between approximately0.0005 to 0.005 inches, approximately 0.0015 to 0.0035 inches, andapproximately 0.0025 inches. The thickness can be about 0.0015 inches.

In the method, the first and second articles can be made of dissimilarmetals. For example, the first article can be made of iron or an ironalloy and the second article can be made of magnesium or a magnesiumallow, aluminum or an aluminum alloy, or titanium or a titanium alloy.One of the first and second articles can be made of a non-metal (e.g., acarbon-based material such as graphite, for example, a carbon fibermaterial). The first article and second article can be made of materialshaving different anodic indices, for example, the anodic indices differby at least 0.1, 0.2, 0.3, 0.4, 0.5, or more.

The first article can have an anodic index that is less than the secondarticle. The first article may comprise iron or an iron alloy and thesecond article may comprise magnesium or a magnesium alloy. Alternately,the second article may comprise aluminum or an aluminum alloy.

The first article can be a male-part fastener, such as a bolt or screw.In such a method, the bolt can exhibit a tension loss of no more thanabout 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, or less when heatedto a temperature of at least about 125° C. for a period of 800 hours,and a tension loss of no more than about 25%, 20%, 15%, 10%, 5%, or lesswhen subjected to thermal cycle at temperatures between about −40° C.and 80° C. (about −40° F. and 176° F.), for 13 cycles and held at eachtemperature for a period of 3 hours.

Also disclosed is a two-article system having first and second articleshaving surfaces facing one another, in which the two articles havedifferent anodic indices, and further in which the surface of the firstarticle comprises a coating layer formed by curing a coating material onthe surface of the first article, and the surface of the first articleis in contact and secured with the surface of the second article. Thetwo articles exhibit substantially no galvanic corrosion followingexposure to a corrosive environment under standard GMW17026 for a 15year simulated exposure test. In an embodiment of the system, when thecured coating material is present on at least a head of a steel boltmounted to a magnesium coupon, the magnesium coupon exhibits less thanabout 20%, 10%, 5%, 3%, or 1% of pitting as compared to an uncoatedsteel bolt mounted on the magnesium coupon after a 15 year simulatedtest under test procedure GMW17026.

In an embodiment, the coating material is a thermoset material. Thethermoset material can be a cross-linked epoxy coating, such as a fusionbond epoxy material. In an embodiment, the epoxy material comprises acuring agent or hardener. The curing agent or hardener can comprise oneor more of more amines, anhydrides, acids, phenols, alcohols and thiols.In an embodiment, the epoxy material comprises one or more of a fillerand a pigment. The epoxy material can cure in approximately thirtyseconds or less when subjected to a temperature of about 400 to 450degrees Fahrenheit to form the cross-linked epoxy coating.

In an embodiment, the coating material comprises a first coatingmaterial and a second coating material, such that the first coatingmaterial is fully cured to form a first cured layer, and the secondcoating material is applied onto at least a portion of the outer surfaceof the first cured layer to form the coating material.

The second coating material can be a thermoset material, and the firstcoating material can be a fast curing material, such that the secondcoating material cures at a slower rate than the first coating material.In an embodiment, the second coating material is a lubricant. Thelubricant can be one or more of a polyethylene wax, a paraffin wax, acarnauba wax, and a solid lubricant. A solid lubricant can be one ormore of molybdenum disulfide and a fluoropolymer.

In an embodiment, the coating material, when cured, has a substantiallyuniform thickness of about 0.0001 to 0.005 inches. The thickness of thethermoset coating can be about 0.005 inches or less, about 0.0035 inchesor less, about 0.0025 inches or less, about 0.0015 inches or less, about0.0010 includes or less, or about 0.0005 inches or less. In variousembodiments, the thickness is between approximately 0.0005 to 0.005inches, approximately 0.0015 to 0.0035 inches, and approximately 0.0025inches.

In a system, the first and second articles are dissimilar metals. One ofthe first and second articles can be a non-metal. The first article canbe a steel bolt and the second article is formed from a metal having alesser anodic index. The second article can be formed from magnesium andthe cured coating material can be present on at least a head of thesteel bolt, such that when mounted to a magnesium coupon, the magnesiumcoupon exhibited less than about 20%, 10%, 5%, 3%, or 1% of pitting ascompared to an uncoated steel bolt on the magnesium coupon, when thecoupon with the uncoated steel bolt exhibited pinhole perforation (orthrough-wall perforation) following 15 year simulated exposure testingunder test procedure GMW17026.

In an embodiment, the first article has an anodic index that is greaterthan the second article. The first article can comprise iron or an ironalloy. The second article can comprise magnesium or a magnesium alloy oraluminum or an aluminum alloy.

In a system the first article is a male-part fastener. The male-partfastener can be a bolt or screw. In such a system the screw exhibits atension loss of no more than about 50%, 45%, 40%, 35%, 30%, 25%, 20%,15%, or 10% when heated to a temperature of at least about 125° C. for aperiod of at least about 800 hours, and a tension loss of no more thanabout 25%, 20%, 15%, 10%, 5%, or less when subjected to thermal cycle attemperatures between about −40° C. and 80° C. (about −40° F. and 176°F.), for 13 cycles and held at each temperature for a period of 3 hours.

In an embodiment, the first article is a steel bolt and the coatinglayer is present on at least a head and an underside of the head of thesteel bolt. Optionally, if the bolt includes a flange, the coating maybe present on at least a portion of the flange. Optionally, the coatingmay be present on at least a portion of the threads of the bolt on thebolt shank.

Other objects, features, and advantages of the disclosure will beapparent from the following description, taken in conjunction with theaccompanying sheets of drawings, wherein like numerals refer to likeparts, elements, components, steps, and processes.

BRIEF DESCRIPTION OF THE DRAWINGS:

The patent or application file contains at least one drawing executed incolor. Copies of this patent or patent application publication withcolor drawing(s) will be provided by the Office upon request and paymentof the necessary fee. Exemplary embodiments of the disclosure will nowbe described by way of example only and with reference to theaccompanying drawings, in which:

FIG. 1 is a schematic illustration of an example of a fastener having athermoset coating thereon, the fastener shown with a panel and anunderlying structure in a partially exploded view for ease ofillustration;

FIG. 2 illustrates two example articles of this disclosure, one withoutany coatings and one with a thermoset coating applied to a portionthereof;

FIG. 3 shows a view of a cross-sectioned example article of thisdisclosure after a thermoset coating was applied;

FIG. 4 shows an illustration of an example article coated with adifferent thermoset coating that is not as consistent in regard tothickness as the thickness of the present thermoset coating;

FIG. 5 illustrates an example production setup for performing certainembodiments of the processes of this disclosure;

FIGS. 6A, 6B and 6C show illustrations of example components of anassembly of this disclosure, or assembled components of the exampleassembly, where FIGS. 6A and 6B provide views of a non-thermoset coatedarticle configured to be fastened to a coated article as illustrated inFIG. 6C;

FIG. 7 is a photograph of a testing assembly in which two sample steelbolts are mounted to a carbon fiber sample panel, the bolt in the bottomof the figure having a thermoset coating according to an embodiment ofthe preset disclosure and the bolt in the top of the figure having nosuch coating;

FIG. 8 is table showing the relative anodic indices of various commonlyused materials, in which the least noble material are shown at the topof the table and the more noble materials are shown at the bottom of thetable;

FIGS. 9A-9G are photographs visually illustrating the results ofcorrosion testing simulated at 1, 2, 3, 4, 5, and 8-9 year simulatedexposure of undistressed uncoated bolts (right-hand side) andundistressed thermoset coated bolts (left-hand side) in a magnesiumcoupon, in a corrosive environment under standard GMW17026, in whichFIG. 9A illustrates the bolts and coupon prior to testing, FIG. 9Billustrates the bolts and coupon at a simulated 1 year exposure, FIG. 9Cillustrates the bolts and coupon at a simulated 2 year exposure, FIG. 9Dillustrates the bolts and coupon at a simulated 3 year exposure, FIG. 9Eillustrates the bolts and coupon at a simulated 4 year exposure, FIG. 9Fillustrates the bolts and coupon at a simulated 5 year exposure, andFIG. 9G illustrates the bolts and coupon at a simulated 8-9 yearexposure;

FIG. 10 is a photograph of a magnesium coupon with an undistresseduncoated bolt (right-hand side) and an undistressed thermoset coatedbolt (left-hand side) mounted to a coupon, following 15 year simulatedexposure texting in a corrosive environment under standard GMW17026;

FIGS. 11A-11L are photographs visually illustrating the results ofcorrosion testing simulated at 1, 2, 3, 4, 5, 10, 11, 12, 13, 14 and 15year exposure of a carbon fiber coupon with undistressed uncoated bolts(left-hand side) and undistressed thermoset coated bolts (right-handside) mounted to coupons in a corrosive environment under standardGMW17026, in which FIG. 11A illustrates the bolts and coupon prior totesting, FIG. 11B illustrates the bolts and coupon at a simulated 1 yearexposure, FIG. 11C illustrates the bolts and coupon at a simulated 2year exposure, FIG. 11D illustrates the bolts and coupon at a simulated3 year exposure, FIG. 11E illustrates the bolts and coupon at asimulated 4 year exposure, FIG. 11F illustrates the bolts and coupon ata simulated 5 year exposure, and FIG. 11G illustrates the bolts andcoupon at a simulated 10 year exposure, FIG. 11H illustrates the boltsand coupon at a simulated 11 year exposure, FIG. 11I illustrates thebolts and coupon at a simulated 12 year exposure, FIG. 11J illustratesthe bolts and coupon at a simulated 13 year exposure, FIG. 11Killustrates the bolts and coupon at a simulated 14 year exposure andFIG. 11L illustrates the bolts and coupon at a simulated 15 yearexposure; and

FIGS. 12A-12L are photographs visually illustrating the results ofcorrosion testing simulated at 1, 2, 3, 4, 5, 10, 11, 12, 13, 14 and 15year exposure of a carbon fiber coupon with distressed uncoated bolts(right-hand side) and distressed thermoset coated bolts (left-hand side)mounted to coupons in a corrosive environment under standard GMW17026,in which FIG. 12A illustrates the bolts and coupon prior to testing,FIG. 12B illustrates the bolts and coupon at a simulated 1 yearexposure, FIG. 12C illustrates the bolts and coupon at a simulated 2year exposure, FIG. 12D illustrates the bolts and coupon at a simulated3 year exposure, FIG. 12E illustrates the bolts and coupon at asimulated 4 year exposure, FIG. 12F illustrates the bolts and coupon ata simulated 5 year exposure, and FIG. 12G illustrates the bolts andcoupon at a simulated 10 year exposure, FIG. 12H illustrates the boltsand coupon at a simulated 11 year exposure, FIG. 121 illustrates thebolts and coupon at a simulated 12 year exposure, FIG. 12J illustratesthe bolts and coupon at a simulated 13 year exposure, FIG. 12Killustrates the bolts and coupon at a simulated 14 year exposure andFIG. 12L illustrates the bolts and coupon at a simulated 15 yearexposure.

DETAILED DESCRIPTION OF EMBODIMENTS

While the present disclosure is susceptible of embodiment in variousforms, there is shown in the drawings and will hereinafter be describedone or more embodiments with the understanding that the presentdisclosure is to be considered illustrative only and is not intended tolimit the disclosure to any specific embodiment described orillustrated.

In the following description of various examples of articles, coatings,assemblies, and components thereof, or processes for making any of thesame, in this disclosure, reference is made to the accompanyingdrawings, which form a part hereof, and in which are shown by way ofillustration various example structures and environments in whichaspects of the disclosure may be practiced. The present disclosure usesseveral definitions, as set forth below and throughout the application.

It is to be understood that other structures and environments may beutilized and that structural and functional modifications may be madefrom the specifically described structures and methods without departingfrom the scope of the present disclosure. Moreover, the figures of thisdisclosure may represent the scale and/or dimensions according to one ormore embodiments, and as such contribute to the teaching of suchdimensional scaling. However, those skilled in the art will readilyappreciate that the disclosure herein is not limited to the scales,dimensions, proportions, and/or orientations shown in the figures.

The embodiments, apparatuses and methods described herein provide, interalia, a system in which at least two articles of dissimilar materials,such as any of the materials shown in the table of FIG. 8 are in contactwith or close proximity to one another, and in which at least one of thearticles is at least partially coated with a material capable ofpreventing galvanic corrosion from occurring. Such a system can be, forexample, assemblies having two dissimilar metals in contact with oneanother, or a metal in contact with a non-metal, such as a carbon fibermaterial or the like, in the presence of an electrolyte. A method forpreventing galvanic corrosion in such a system is also disclosed. Innon-limiting examples, a steel component such as a steel bolt, ispartially or entirely coated with a material that is capable ofpreventing galvanic corrosion from occurring, which bolt is used tosecure a chrome article, a magnesium article, an aluminum article, astainless steel article, or a carbon fiber article, such as a pan, panelor applique, to a structure, such as casing, or an underlying structure,without adversely affecting the mechanical properties, requirements,conditions and specifications of the system. It will be appreciated thatthe present method and system protect, for example, underlyingcomponents, such as magnesium oil pans when secured to a casing usingsteel bolts, and protect steel bolts when used to secure carbon fiberpanels to an underlying structure, noting that, as seen in FIG. 8, steelis at about a mid-point of the anodic index and magnesium and carbonfiber are at extreme opposite ends of the anodic index spectrum.

These and other aspects, features and advantages of the disclosure or ofcertain embodiments of the disclosure will be further understood bythose skilled in the art from the following description of exemplaryembodiments. Amongst other advantages, the coated articles of thisdisclosure may be produced very quickly via a high volume manufacturingprocess, have a high strength/durability/scratch resistance, and may beable to withstand elevated temperatures for extended time periods. Inaddition, the coated articles exhibit good resistance to chemicals foundin automotive applications, such as motor oil, fuels (diesel, gasoline,bio-based and compounded fuels such as ethanol based fuels), powersteering fluid, windshield washer fluid and the like.

In accordance with one exemplary aspect, a metal article comprising atleast a first surface is disclosed, the first surface being at leastpartially covered by a thermoset coating.

FIG. 1 illustrates one such example. In FIG. 1, a coated bolt 1 is usedto secure a panel P, such as a transmission oil pan, to a transmissioncasing C. In FIG. 1, the head 2 of the bolt 1, the flange 3 of the bolt1 and a portion 4 of the shank 5 having the thermoset coating 6 appliedthereto. The bolt 1 can be formed from steel, the panel or pan P formedfrom magnesium and the underlying structure or the casing C formed fromaluminum. It will be appreciated that the magnesium pan P issignificantly more anodic than the steel of the bolt 1, and thussusceptible to galvanic corrosion. In the illustrated example, thecoating 6 is present over the head 2 and flange 3 and partially 4 alongthe threads on the shank 5 of the bolt 1, and thus provides a barrierbetween the bolt 1 and the pan P to prevent and/or inhibit galvaniccorrosion. It will be appreciated that the extent of the coating can bemore or less, depending upon the application.

FIG. 2 provides other illustrative examples of coated and non-coatedarticle. In FIG. 2, non-coated article 10 (in this example, a differentform of bolt) has a threaded portion 14 and a fastening assembly 12configured to accept a second article, the fastening assembly comprisinga first wear surface 16, a second wear surface (in this example, thehead of the bolt) 18 and a connecting portion 17. In this example,surfaces of the fastening assembly are configured to come into contactwith an article made of a dissimilar metal. FIG. 1 also shows a coatedarticle 20, wherein a portion of the article has a thermoset coating.While in some examples the article is entirely covered by the thermosetcoating while in others only a portion or portions of the article arecoated. In the example of FIG. 2, the entire fastening assembly 22 ofcoated article 20 is covered with the thermoset coating, including thethreaded portion 24, providing coated wear surfaces 26 and 28 and acoated connecting portion 27. It should, however, be noted that in someexamples, the threaded portion 24 may not be coated.

As a representative example, the coated article may be connected to orincorporated in a larger assembly through or by the non-coated portion,such as threaded portion 24 here, and then another metal or non-metalcomponent having a different galvanic or electro-potential or anodicindex is connected or fastened to the fastening assembly. The fasteningassembly may have any appropriate size, geometry, or configuration asneeded based on the parts that are to be joined together. In manyexamples, the article comprises one or more recesses, hollows, channels,cavities, or other features configured to interact with or fastener toan appropriate feature on a second article, where the interior of therecess(es) etc. are coated with one or more coatings. In other examples,the coated article does not have a fastening assembly of any kind, butis rather configured to simply be in contact with a dissimilar metal ornon-metal component having a different galvanic or electro-potential oranodic index such that galvanic corrosion may otherwise occur withoutthe thermoset coating.

In the illustrative example of FIG. 2, the primary wear protection isneeded at the slot defined by and between portions 26 and 28, where, forexample, a chrome-plated applique component is ultimately slid into theslot between the two flat plates. In some examples, such as the coatedarticle 20 of FIG. 2, any and all surfaces of components that act aswear surfaces are coated by the thermoset coating (or coatings, asdescribed in more detail below), while in others only the particularwear surfaces are coated. To use the coated article 20 as an example,other embodiments may only apply coatings to the interior surfaces ofthe fastening assembly 22 that define or are within the slot, andultimately come into contact with the dissimilar metal or non-metalcomponent having a different galvanic or electro-potential or anodicindex, and not the outward facing surfaces of the same components.

The articles, assemblies, systems, and methods disclosed herein includeor utilize a thermoset material as a coating. As would be understood inthe art, a thermoset material comprises a prepolymer which curesirreversibly after exposure to heat, generally above 392 F, chemicalreaction, and/or suitable irradiation. Accordingly, the thermosetmaterial included in or utilized by the articles, assemblies, systems,and methods disclosed herein may be cured by any suitable meansincluding heat, chemical reaction, and/or suitable irradiation. Suitableheating methods for curing the thermoset material may include, but arenot limited to, subjecting the thermoset material to heat generated byinduction. Examples of suitable thermoset materials for use in thedisclosed articles, assemblies, systems, and methods may include, but isnot limited to, epoxy materials such as epoxy resins or polyepoxides,polyester or polyester resin material, polyurethane material, vulcanizedrubber material, phenol-formaldehyde resin material such as Bakelite,melamine material, diallyl-phthalate (DAP) material, polyimide material,and cyanate ester or polycyanurate material. Optionally, the thermosetmaterial may include a prepolymer and a hardener (e.g., a co-reactantincluding polyfunctional amines, acids (and acid anhydrides), phenols,alcohols and/or thiols).

In various examples, the thermoset coating is a rapid-cure thermosetcoating. In certain embodiments, the rapid-cure thermoset coatingmaterial cures in about one minute or less when exposed to an inductionheater while the coating material in contact with the metal article,while in others it cures in approximately thirty seconds or less. Insome examples, the coating cures in either of the above time periods (orothers) when exposed to temperatures between about 350 degrees to 475degrees Fahrenheit. In some examples, the coating material cures inapproximately thirty seconds or less when subjected to a temperature ofabout 400 to 450 degrees Fahrenheit, in others about 350 to 490 degreesFahrenheit, while in others about 420 to 430 degrees Fahrenheit, whilein still others about 425 degrees Fahrenheit, after being applied as apowder to the article.

In various examples, the thermoset coating comprises an epoxy materialsuch as an epoxy resin material or polyepoxide material. The epoxy resinmaterial of the thermoset coating may be reacted (cross-linked) eitherwith itself through catalytic homopolymerization, or with a wide rangeof co-reactants including polyfunctional amines, acids (and acidanhydrides), phenols, alcohols and thiols. These co-reactants may behardeners or curatives, and the cross-linking reaction may be referredto as “curing.” Suitable epoxy resin materials for the thermoset coatingmay include, but are not limited to, bisphenol A epoxy resin material(e.g., as produced by combining epichlorohydrin and bisphenol A to givebisphenol A diglycidyl ethers), bisphenol F epoxy resin material, epoxyphenol novolac material and epoxy cresol novolac material (e.g., asproduced by reaction of phenols with formaldehyde and subsequentglycidylation with epichlorohydrin), aliphatic epoxy resin material(e.g., as produced by glycidylation of aliphatic alcohols or polyols),and glycidylamin epoxy resin material (e.g., as formed when aromaticamines react with epichlorohydrin).

In various examples, the thermoset coating is a cross-linked epoxycoating. The coating may be a fusion-bond epoxy coating. In someembodiments, the thermoset coating is made from a powder, such as anepoxy powder, that is subsequently cured/cross-linked to form thethermoset coating, while in others it is made from a liquid precursor.In various examples, the coating is made from a powder comprising anepoxy resin and one or more curing agents or hardeners. The curingagents or hardeners may consist of or comprise one or more amines (e.g.aromatic amines, aliphatic diamines), anhydrides, acids, phenols,alcohols and/or thiols. In some examples, the powders further compriseone or more fillers and/or one or more pigments, or other additionalcomponents. In certain examples using fusion-bond epoxy coating, thethermoset coating is made from 3M® Fusion Bonded Epoxy 413, 3M®Scotchkote 426 FAST, and/or Axalta Alesta 74550.

The cross-linked thermoset coating provides high strength and durabilityfor use in applications where the coating is exposed to abrasion forces,for example providing higher durability than nylon coatings and/orthermoplastic coatings that are known in the art. Use of certain epoxiesidentified above may also advantageously provide strong adhesion to thearticle substrate (as compared to nylon thermoplastic coatings), goodresistance to impact and/or improved scratch/abrasion resistance. Forexample, example articles having 3M® Fusion Bonded Epoxy 413 to form thethermoset coating revealed, based on microscopy analysis, only topsurface scratches after repeated insertions by components that couldresult in removal of nylon thermoplastic coatings in areas that cameinto contact with the articles.

In various embodiments, the article further comprises a lubricantcoating in contact with at least a portion of the article. In someexamples, the lubricant coating covers or is in contact with at least aportion of the thermoset coating, while in others it covers the entirearticle and/or the entire surface of the thermoset coating. In someexamples, the lubricant is applied to surfaces, such as on bolt threadsand bearing surfaces that are exposed to forces during use of thearticle, such as a fastener. As one representative example, the coatedarticle 20 shown in FIG. 2 may have lubricant coating only on thesurfaces of the fastening assembly (e.g. coated wear surfaces 26 and 28and a coated connecting portion 27) or may only have a lubricant coatingon the surface experiencing the highest forces, in this example theconnecting portion 27. The lubricant may be a solid or liquid lubricant.In some embodiments, the lubricant coating consists of or comprises oneor more waxes, for example one or more polyethylene wax, paraffin waxes,carnauba waxes, a solid lubricant such as molybdenum disulfide, or oneor more a fluoropolymers (e.g. polytetrafluoroethylene). In the bolt ofFIG. 1, the lubricant may be present on the threads 5, to achieve adesired coefficient of friction, and/or on the underside of the flange3.

In some examples, the thermoset coating has a substantially uniformthickness. In various embodiments, the coating thickness (regardless ofthe geometry and/or shape of the article) only deviates from about 0.002inches or less from the overall average coating thickness, while inothers about 0.001 inches or less, in still others about 0.0005 inchesor less. In certain embodiments, the thermoset coating thickness isabout 0.005 inches, inches or less, while in others it is approximately0.0035 inches or less, or approximately 0.0025 inches or less, orapproximately 0.0015 inches or less, or approximately 0.0010 includes orless, or approximately 0.0005 inches or less. In various embodiments,the thickness is between approximately 0.0005 to 0.005 inches,approximately 0.0015 to 0.0035 inches, and approximately 0.0025 inches.

In certain examples, the article comprises an inorganic coating, such aceramic coating, and/or is electroplated and/or plasm-trerated, forexample the article may comprise a Keronite® coating. In some examples,an aluminum article is coated with the Keronite® coating, where it maybe used in conjunction with a magnesium article, which, as a skilledartisan would understand, is pre-disposed to galvanic corrosion givenits position on the anodic index. By coating the aluminum fastener,which will act as the cathode, these examples provide a barrier toprevent galvanic corrosion, even with a material such as magnesium. Thisadvantageously allows coupling of magnesium parts without the use ofexpensive components as is currently known in the art. Moreover, bycoating the aluminum cathode, these example may avoid potential problemsresulting from coating the magnesium component, as any minute hole inthe magnesium's coating results in galvanic corrosion in a concentratedareas of the magnesium (as it degrades by virtue of being the anode inthe galvanic cell) which can detrimentally weaken structural integrityof the part, especially if the concentrated corrosion is at an importantlocation of the part. In yet other examples, a magnesium surface may becoated as described here, for example with a ceramic coating, and insome examples, both an aluminum piece and a magnesium piece may becoated and used together, to further inhibit the possibility ofcorrosion. Any of these examples may also comprise one or more of thethermoset coatings described herein and/or one or more lubricantcoatings on top of the, e.g., ceramic coating. This may result inadditional benefits when the inorganic coating is somewhat porous orotherwise has surface irregularities (but still provides a coatingsufficient to prevent galvanic corrosion). For example, a Keronite®ceramic coating has pores that may be filled with the thermoset coatingto help promote adhesion and provide a more comprehensive galvanicbarrier.

In certain examples, the thermoset coated article has a heat resistancesuch that it may be exposed to elevated temperatures for extended timeperiods without adverse effects to the coating, such as softening,melting, flowing, dripping, charring and the like. For example, incertain embodiments the coated article is capable of withstandingapproximately 350 degrees Fahrenheit for approximately thirty minuteswithout adverse effects to the coating. The epoxy thermoset resinsidentified above, for example 3M® Fusion Bonded Epoxy 413, 3M®Scotchkote 426 FAST and/or Axalta Alesta 74550, provide coatings havingthese improved levels of heat resistance, meaning the coatings will notmelt and/or flow out when exposed to these types of heat conditions.This can, for example, be helpful in embodiments where the coatedarticle is exposed to additional manufacturing processes. A steel clipdesigned to hold an aluminum fender to an automobile body is one exampleof such an embodiment, as these components may be exposed to elevatedtemperatures (including the thirty minute, 350 degree Fahrenheitconditions noted above) during production of the automobile.

FIGS. 3 and 4 provide example views of articles coated with examplematerials 3M® Fusion Bonded Epoxy 413 (FIG. 3) and 3M® Scotchkote 426FAST (FIG. 4). In the example of FIG. 3, a steel fastener 30A was coatedwith a layer of 3M® Fusion Bonded Epoxy 413 and heated to curetemperature via induction heat, providing a substantially uniformthermoset coating 32A (the outer material). In the example of FIG. 4, asteel fastener 30B was coated with a layer of 3M® Scotchkote 426 FASTand heated to cure temperature via induction heat (requiring a highercure temperature as compared to the example shown in FIG. 3, e.g. aboutdegrees 450 degrees Fahrenheit compared to about 425 degreesFahrenheit), providing thermoset coating 32B (the outer material, whichdoes not have as uniform of a thickness when compared to the example ofFIG. 3).

In some embodiments, the article is a fastener, for example a bolt, clipor shank. The article may consist of or comprises any metal or metallicalloy. In certain embodiments, the article is steel. In others, such asbut not limited to the articles that also comprise a ceramic coating, itis magnesium, aluminum, titanium, or alloys thereof. In some examples,the article consists or comprises steel, stainless steel, titanium,nickel, copper, bronze, brass, tin, lead, iron, aluminum, zinc,magnesium, or alloys thereof. Such a clip may be, for example, a steelclip that may be used to mount an aluminum fender onto a vehicle. Such aclip may be entirely coated with the example 3M® Fusion Bonded Epoxy413, 3M® Scotchkote 426 FAST and/or Axalta Alesta 74550, but othercross-linked thermoset resins would be useable as described herein, orit may be partially coated, for example on a single surface or a subsetof all the surfaces.

In certain examples, the thermoset coating comprises a first thermosetcoating, and a second thermoset coating is applied to the article on topof the first thermoset coating, a portion thereof, or the entire surfaceof the article, including any portions already covered by the firstthermoset coating. In various examples, the first thermoset coating is arapid-cure thermoset coating and the second thermoset coating is not arapid-cure thermoset coating. For example, in some embodiments the firstthermoset coating cures in about one minute or less when exposed to aninduction heater while in contact with the metal article, while thesecond thermoset coating requires a longer cure time at an equivalenttemperature range used for curing the first thermoset coating, forexample ten minutes or more, or fifteen minutes or more. In someexamples, the second thermoset coating comprises one or more epoxies,polyesters or polyurethanes, while in others the second coatingcomprises an epoxy/polyester mixture. In one example, the secondthermoset coating is made from a Valspar® TGIC polyester powdered (suchas PRA60001).

As one example, the polyester material, when applied as the solecoating, had poor impact resistance when coated onto a steelfastener—but when applied on top of another thermoset coating, in thisexample the 3M® Fusion Bonded Epoxy 413, the results were surprisinglydifferent. The combined coatings exhibited high impact resistance, evenwhen the polyester material was not completely cross-linked (forexample, because it was only exposed to induction heat for the same oftime used to cure the rapid-cure thermoset resin), and surprisingly hadhigh adhesion despite the incomplete cure to the lower thermosetcoating, such as an epoxy.

Therefore, in various examples, the second thermoset coating isonly-partially cross-linked, for example when it is exposed to heat fora period of time shorter than necessary to achieve full curing. Thisadvantageously still allows traditionally slower curing materials to beincorporated into a high speed, high volume manufacturing process whendesired, but still providing an improved and strengthened coatedarticle. In certain of these examples, the base, rapid-cure thermosetcoating material is applied, quickly cured via heat such as inductionheat, and then the second coating material was applied and partiallycured (or, in some examples, entirely cured despite the longer curetimes needed). These examples comprising a second thermoset coating mayalso comprise the lubricant coating.

These descriptions of the article are merely exemplary. In certainembodiments, the article comprises additional combinations orsubstitutions of some or all of the components described above.Moreover, additional and alternative suitable variations, forms andcomponents for the article will be recognized by those skilled in theart given the benefit of this disclosure.

Other aspects of the disclosure relate to an assembly. The assembly maycomprise a first article and a second article configured to be fastened,connected, or in close proximity to the first article, wherein the twoarticles have dissimilar electro-potentials (anodic indices) such thatgalvanic corrosion may occur when the articles are in the presence of anelectrolyte. The first article may be partially or entirely coated withone or more thermoset coatings, such as any of the coatings describedabove or elsewhere in this disclosure, and optionally a lubricantcoating.

In certain examples, the second article comprises, is connected to, oris configured to be connected to a third article (such as an automobileor a component thereof). Assemblies having an article with one or morecoatings as described herein may comprise automotive or aerospacematerials such as, fasteners, clips or other connection materials. Stillother possible articles for use in the assemblies may be a fastener fora decorative automotive applique, or other automotive material such asbut not limited to a fastener, clip or securing article for use with afender or an oil pan, including a magnesium oil pan. For example, FIG. 6shows illustrations of an applique assembly, where FIGS. 6A and 6Bprovide views of a non-coated article, a chrome-plated applique 38,configured to be fastened to a coated fastener as shown in FIG. 6C,where the fastener is identical or substantially similar to the coatedarticle 20 from FIG. 2.

FIG. 7 is a photograph that illustrates an example in which two samplesteel bolts are mounted to a carbon fiber sample panel following asimulated 15 year test in a corrosive environment under standardGMW17026. The upper bolt in the photograph is not coated with thethermoset coating, whereas the lower bolt in the photograph is coatedwith the thermoset coating. It is readily apparent that there issignificant corrosion of the uncoated bolt and that there is little tono corrosion exhibited by the thermoset material coated bolt. It willthus be appreciated that the sample bolts in the photograph illustratethe significant corrosion resistance provided by the present thermosetcoating.

These assembly descriptions are merely exemplary. In certainembodiments, the assembly comprises additional combinations orsubstitutions of some or all of the components described above.Additional and alternative suitable variations, forms and components forthe assemblies will be recognized by those skilled in the art given thebenefit of this disclosure. Moreover, any of the features discussed inthe exemplary embodiments of the article described above may be featuresof embodiments of the assembly or components thereof, and vice versa.

Still other aspects of the disclosure relate to a process. In someexamples, the process comprises applying a powder coating to an article(for example by spraying the powder coating onto the article). Thepowder precursor material may be suspended in a stream of air andsprayed onto the article using suitable spray guns, which may ionize thepowder so that the powder properly coats the metal article prior tocuring. In some embodiments, a tribo charging process is used to ensurethe recessed or other difficult to reach areas properly receive thepowder coating, as use of heavy electrostatic forces results in a cageeffect that prevents the powder from coating these areas as needed. Incertain examples, a powder goes through a thermoplastic material in thespray gun to achieve the desired charge. Other application methods arepossible, however, for example the article may be dipped into a bed ofthe powder precursor. For embodiments where difficult to reach surfacesor internal surfaces need to be coated, additional spray gun attachmentsor extensions may be used. In other examples, a shield or shields may bepositioned between the spray gun and the articles such that only acertain portion or portions of the article to be covered in powder (andtherefore, ultimately, coated by the thermoset coating). In certainexamples, the article is cleaned and/or scratched and/or otherwiseprimed to promote adhesion of the coating precursor material prior tocuring.

The process may also comprise heating the powdered article. In someexamples, the process may comprise transporting the powdered article toa heat source, such as an induction heater applying a magnetic field. Incertain examples, a metal article is at room temperature or ambienttemperature, the powder is applied to the metal article, and then thearticle and powder are heated, for example by exposure to an inductionheater, such that the powder cures into a cross-linked thermosetcoating. In other examples, the article may be heated in the samelocation where the powder is applied, or the article may be heated priorto application of the powder, so any residual heat in the metal providesthe cure or at least partially cures the powder. Embodiments of theprocess where the powder is applied to a room temperature article arepreferred, however, given the relative simplification of themanufacturing process provided.

The articles may be transported (for this step or otherwise) using anyknown conveyance system in the art, such as a conveyor belt, one or moregripper wheels, a rotary bench, or, as in the example illustrated inFIG. 5, a magnetic table 50. In some examples, the conveyor brings thearticles inside and through a heat source, such as an induction heater52. In other examples, one of more components may be moved ortransported into proximity to the article, which remains stationary,such as a powder spray gun 46 where the powder 48 is applied to thearticles. An air stream (not shown) may be used to blow off excessmaterial from the articles.

Other possible heating methods include use of infrared heat and/or otherthermal radiation, a curing oven, a heat tunnel, a heat gun, or bringinga heat source into direct contact with the article to transfer heat viaconduction, and the like. The temperature used to cure the powder may beany of those described previously (i.e. between about 350 to 490 degreesFahrenheit, or about 425 degrees Fahrenheit, or others) depending on thecharacteristics of the coating material (e.g. the resin and any curingagent(s) composition) and particular process.

For example, in some embodiments, heat is applied for five or lessseconds, in others ten or less seconds, and in others fifteen seconds orless, thirty seconds or less, sixty seconds or less. In other examples,such as processes using longer-cure materials or lower temperatures,longer times on the order of minutes (e.g. two minutes or less, fiveminutes or less, ten minutes or less, fifteen minutes or less, or thirtyminutes or less) may be needed. Embodiments allowing full cure, ornearly full cure of at least the base thermoset layer on shorter timeranges, however, are preferred given the advantages provided inmanufacturing speed.

The process may further comprise transporting the coated article to alubricating station, where one or more lubricants (e.g. a polyethylenewax emulsion) are applied to the article, for example through sprayingor dipping. The process may also comprise drying the lubricated article,for example through another application of induction heating or use ofanother heat source (or even the same heat source used to cure the resininto a cross-linked material). In various examples, additional heat isnot provided and the articles air dry, or no drying is needed based onthe choice of lubricant (e.g. when a dry lubricant such as molybdenumdisulfide is used). In some embodiments, a shorter application of heatis all that is necessary to dry the lubricated article, for example aone to two second application of induction heat. This helps further themanufacturing efficiencies of the process.

In some examples, prior to lubrication, a second thermoset coatingmaterial is applied and at least partially cured on the article. Incertain examples, the process may comprise forming a ceramic coating onthe article, and then applying one or more thermoset coatings (forexample, a rapid-cure then a non-rapid cure thermoset coating) and thenoptionally applying one or more lubricant coatings.

As noted above, FIG. 5 illustrates an example system for performingembodiments of the method. In this example, the system comprises amagnetic table holding and transporting a plurality of articles, whichare at room temperature in these embodiments. In step A of this exampleprocess, a spray gun applies the powder precursor material (e.g. thepowdered epoxy) to the article, which is then conveyed to a locationbetween induction heaters. In step B, the heater applies heat to curethe powder and result in a cross-linked thermoset coating on thearticle. Optionally, the magnetic table then conveys the coated articlesto a lubricant applicator, such as a spray gun, which applies thelubricant in step C. Then the magnetic table conveys the finishedarticles to a finish location for removal from the table in example stepD. It will be appreciated that the process permits selectively applyingthe coating to, for example, the head of the bolt, the head and flange(if present) of the bolt, the underside of the head and, if desired, tothe threads or a portion of the threads of the bolt.

Various samples of assemblies were tested to determine the effectivenessof coating one of two articles of the assembly with a material that iscapable of preventing galvanic corrosion. The material that was coatedonto the articles was a fusion bonded, cured, thermoset polymericmaterial, Axalta Alesta 74550, applied using a tribo charge process to athickness of about 0.0025 to 0.0035 inches when cured. All of thetesting was conducted using M10 fasteners (bolts) with a 10 micronDipzol NZ-200 alkaline plating secured to magnesium and carbon fiberpanels. The tests included accelerated corrosion testing in accordancewith General Motors Worldwide Engineering Standards test procedureGMW17026, “Accelerated Corrosion Laboratory Test for Galvanic CorrosionMechanisms” (corrosion testing), tension loss testing and physicalmeasurements to determine adequacy of coating relative to mechanicalrequirements of the assembly.

The corrosion testing was carried out using bolts mounted to samplepanels (coupons) of magnesium and carbon fiber. One of the bolts on eachcoupon was coated with a fusion bonded, cured, thermoset polymericmaterial and a control bolt on each coupon was uncoated. The couponswere positioned on a plastic grid in a stainless steel chamber andsubjected to a direct spray of a solution of 3% salt, 3% fire clay and94% water at a temperature of 66° C. (about 150.8° F.) for 2 minutesevery 3 hours. The spray was applied at a rate of about 2.5 liters (L)per minute per nozzle. The coupons had an initial thickness of about 3millimeters (mm) prior to exposure to the spray solution.

The corrosion testing simulated 1, 2, 3, 4, 5, and 8-9 year exposure ofthe magnesium coupons by subjecting the coupons to spray for 5 days (1year simulation), 10 days (2 year simulation), 15 days (3 yearsimulation) through 35 days (8-9 year simulation). The testing wassuspended after 35 days (8-9 year simulation) as the nut on securing thecontrol bolt corroded through the magnesium coupon. Photographs showingthe visual results of the testing are provided in FIGS. 9A-9G, in whichFIG. 9A shows the coated and uncoated bolts, on the left-hand side andright-hand side of the photographs, respectively, unexposed or prior totesting, and FIGS. 9B-9G show the bolts after 1 year, 2 year, 3 year 4year, 5 year and 8-9 year simulated exposure. As will be readilyapparent from the photographs, the magnesium coupon with the coated boltexhibited little to no signs of corrosion after 35 days (8-9 yearsimulation) in the corrosion test chamber, whereas the coupon on whichthe uncoated was mounted exhibited extreme corrosion and, as notedabove, required that the testing be suspended due to failure of thecoupon (magnesium) material as a result of contact of the coupon with anuntreated nut on the rear side of the coupon. In this case, galvaniccorrosion occurred in the magnesium coupon in that magnesium is moreactive, or less noble, than the steel and thus serves as the anode inthe galvanic reaction.

FIG. 10 is a photograph showing a coupon after simulated 15 yearexposure of the magnesium coupon. As can be readily seen, at 15 yearsimulated testing, the area of the coupon around the thermoset coatedbolt exhibited essentially no pitting, whereas the area of the couponaround the uncoated bolt exhibited extreme pitting and was found to havepitted through (through the 3 mm thickness of the coupon).

At the suspension of the test at 35 day simulation, the coupons with theuncoated bolts had thoroughly pitted through (pitting of about 3 mm), ashad the coupon at 15 year simulated testing, while the coupons with thecoated bolts had pitted less than about 0.089 mm, or less than about 3%of the uncoated bolts.

A similar corrosion test was conducted using undistressed anddistressed, uncoated and coated bolts mounted to sample panels (coupons)of carbon fiber. The corrosion testing simulated 1, 2, 3, 4, 5, 10, 11,12, 13 14 and 15 year exposure of the magnesium coupons by subjectingthe coupons to spray for 5 days (1 year simulation), 10 day (2 yearsimulation), 15 days (3 year simulation) through 65 days (15 yearsimulation). In the testing of the distressed bolts, 1 kg (about 2.2lbs.) of bolts were placed in a hopper mounted to the top of a 150 mm(about 6 inch) tube about 1 meter (39 inches) high. A trap door at thebase of the hopper was opened to allow the bolts to fall (about 39inches) into a non-metal collection box. The drop procedure was repeatedthree times prior to removing the bolts for testing.

Photographs showing the visual results of the testing of thenon-distressed bolts are provided in FIGS. 11A-11L, in which FIG. 11Ashows the coated and uncoated bolts, on the left-hand side andright-hand side of the photographs, respectively, unexposed or prior totesting, and FIGS. 11B-11L show the bolts after 1 year, 2 year, 3 year 4year, 5 year, 10 year, 11 year, 12 year, 13 year 14 year and 15 yearsimulated exposure. Again, as will be readily apparent from thephotographs, the coated bolt on the carbon fiber panel exhibitedsignificantly less signs of corrosion after 65 days (15 year simulation)in the corrosion test chamber, whereas the uncoated bolt on the carbonfiber panel exhibited extreme corrosion. An examination of thephotographs (and particularly FIG. 11L) shows that the coated boltedexhibited superficial discoloration with limited spread to the carbonfiber panel to which it was mounted, whereas the uncoated bolt exhibitedwhat appears to be significant structural degradation and significantspreading onto the carbon fiber panel.

Photographs showing the visual results of the testing of the distressedbolts are provided in FIGS. 12A-12L, in which FIG. 12A shows the coatedand uncoated bolts, on the right-hand side and left-hand side of thephotographs, respectively, unexposed or prior to testing, and FIGS.12B-12L show the bolts after 1 year, 2 year, 3 year 4 year, 5 year, 10year, 11 year, 12 year, 13 year 14 year and 15 year simulated exposure.Again, as will be readily apparent from the photographs, the coated bolton the carbon fiber panel exhibited significantly less signs ofcorrosion after 65 days (15 year simulation) in the corrosion testchamber, whereas the uncoated bolt on the carbon fiber panel exhibitedextreme corrosion. An examination of the photographs (and particularlyFIG. 12L) shows that the coated bolted exhibited superficialdiscoloration with limited spread to the carbon fiber panel to which itwas mounted, whereas the uncoated bolt exhibited what appears to besignificant structural degradation and significant spreading onto thecarbon fiber panel.

In the case of the bolts in the carbon fiber coupons, it must beremembered that galvanic corrosion occurred in the steel bolt, ratherthan the carbon fiber coupons, in that steel is more active, or lessnoble, than carbon fiber and thus serves as the anode in the galvanicreaction.

It will be appreciated that because the bolts, rather than the couponswere subjected to galvanic corrosion, there are no weight lossmeasurements for the coupons. Nevertheless, an examination of thesamples in FIG. 12L shows that while there was significant structuraldegradation and significant spreading onto the carbon fiber with theuncoated bolts, the coated bolted exhibited only superficialdiscoloration with limited spread to the carbon fiber panel to which itwas mounted.

Tension loss tests were also conducted to determine whether the coatingresulted in unacceptably increased tension loss in coated bolts comparedto uncoated (control) bolts, and to bolts coated with a nylon 11 powdercoat. An M-10 uncoated (control) bolt, bolts coated with a thermosetcoating of the present disclosure, and bolts coated with nylon 11 wereplaced in a 19 mm thick steel block. Zinc coated steel washers werepositioned between the head of the bolts and 10 mm steel nuts werethreaded onto the threads of the bolt to secure the bolts to the block.The bolts were tighten to a torque of 45-55 N-m. The assembly, whichincluded all of the bolts was heated to a temperature of 125° C. (about257° F.) for a period of 800 hours. A Dakota Ultrasonics MINI-MAX boltTension Monitor was mounted to each bolt to ultrasonically determine theloss of tension in the bolts. The thermoset coating was applied to thebolts to a thickness of about 0.0025 inches to 0.0035 inches.

The uncoated (control) bolts exhibited a tension loss of about 20%, thebolts coated with a thermoset coating of the present disclosureexhibited a tension loss of about 25% and the bolts coated with nylon 11exhibited a tension loss of about 33% to 65%. A review of the test datashows that the tension loss of the bolts coated with a thermoset coatingof the present disclosure exhibited an acceptably low tension losscompared to the control bolts, whereas the bolt coated with nylon 11exhibited an unacceptably high tension loss.

A thermal cycling test for tension loss of uncoated (control) bolts andbolts coated with a thermoset coating of the present disclosure andbolts coated with a nylon 11 powder coat was also conducted in which thebolts were subjected to thermal cycling between −40° C. and 80° C.(about −40° F. and 176° F.). The bolts were subjected to thermal cyclingbetween −40° C. and 80° C. for 13 cycles and held at temperature for aperiod of 3 hours. The control bolts exhibited tension loss of about18.6%, the bolts with a nylon 11 powder coat exhibited a tension loss ofabout 33.3% to 42.5%, and the bolts coated with a thermoset coatingexhibited a tension loss of between about 4.7% and 14.5%, showing noadverse effects of the thermoset coating on tension loss in thermalcycling.

Bolts coated with a thermoset coating of the present disclosure alsoexhibit a uniform and non-interfering coating. The coating thickness asapplied was about 0.63 mm (about 0.0021 inches) to about 0.89 mm (about0.0029 inches), and when applied to a bolt having a recessed drive head,such as a hex or TORX® drive, does not interfere with engagement of thedrive tip with the drive recess. The coating was also appliedsufficiently along the threads so that the coating was present at thethread engagement, and was found to not interfere with fastening thebolts to a female threaded member. Advantageously, it has also beenfound that the present thermoset coating does not interfere withmagnetism, and as such, the use of magnetic drives and drive tips andmagnetically securing the bolts is unaffected. A depiction of theuniformity and thickness of the coating on a bolt is illustrated in FIG.3.

The bolts were also tested for coefficient of friction, which is thefriction that is exhibited as the bolt is tightened onto an assembly.The coefficient of fiction is a dimensionless value, but corresponds tothe force that must be applied to properly tighten or torque the bolt toa certain value. The coefficient of friction desired for driving thebolts is about 0.10 to 0.16. The coefficient of friction of the coatedbolts was adjusted by use of a lubricant to be about within this range.

These process descriptions are merely exemplary. In certain embodiments,the process may include additional combinations or substitutions of someor all of the steps described above. Moreover, additional andalternative suitable variations, forms and components for the processwill be recognized by those skilled in the art given the benefit of thisdisclosure. Finally, any components or features of the articles and/orassemblies discussed above may be produced by embodiments of theprocess, and any steps or actions described in relation to the articlesand/or assemblies may be incorporated into embodiments of the process.

As used herein, “about,” “approximately,” “substantially,” and“significantly” will be understood by persons of ordinary skill in theart and will vary to some extent on the context in which they are used.Also as used herein, the terms “include” and “including” should beinterpreted to have the same meaning as the terms “comprise” and“comprising” in that these latter terms are “open” transitional termsthat do not limit claims only to the recited elements succeeding thesetransitional terms. The term “consisting of,” while encompassed by theterm “comprising,” should be interpreted as a “closed” transitional termthat limits claims only to the recited elements succeeding thistransitional term. The term “consisting essentially of,” whileencompassed by the term “comprising,” should be interpreted as a“partially closed” transitional term which permits additional elementssucceeding this transitional term, but only if those additional elementsdo not materially affect the basic and novel characteristics of theclaim.

It will further be appreciated by those skilled in the art that therelative directional terms such as sides, upper, lower, rearward,forward and the like are for explanatory purposes only and are notintended to limit the scope of the disclosure.

All patents referred to herein, are hereby incorporated herein byreference, whether or not specifically done so within the text of thisdisclosure. In the present disclosure, the words “a” or “an” are to betaken to include both the singular and the plural. Conversely, anyreference to plural items shall, where appropriate, include thesingular.

It should also be understood that various changes and modifications tothe presently disclosed embodiments will be apparent to those skilled inthe art. Such changes and modifications can be made without departingfrom the spirit and scope of the present disclosure and withoutdiminishing its intended advantages. It is therefore intended that suchchanges and modifications be covered by the appended claims.

What is claimed is:
 1. A method to prevent corrosion of a susceptiblearticle of a two-article system, in which first and second articles ofthe two-article system have surfaces facing one another and in which thetwo articles have different anodic indices, the method comprising:applying a coating material to the surface of the first article; curingthe coating material on the surface of the first article; and contactingand securing the surface of the first article with the surface of thesecond article, wherein the two articles exhibit substantially nocorrosion following exposure to a corrosive environment under standardGMW17026 after a 15 year simulated test.
 2. The method of claim 1wherein the coating material is a thermoset material.
 3. The method ofclaim 2 wherein the thermoset material is an epoxy material that crosslinks during coating to form a cross-linked epoxy coating.
 4. The methodof claim 3 wherein the epoxy material is a fusion bond epoxy material.5. The method of claim 3 wherein the epoxy material comprises a curingagent.
 6. The method of claim 5 wherein the curing agent comprises oneor more of more amines, anhydrides, acids, phenols, alcohols and thiols.7. The method of claim 3 wherein the wherein the epoxy materialcomprises one or more of a filler and a pigment.
 8. The method of claim3 wherein the epoxy material cures in approximately thirty seconds orless when subjected to a temperature of about 400 to 450 degreesFahrenheit to form the cross-linked epoxy coating.
 9. The method ofclaim 1 wherein the coating material is applied as a powder.
 10. Themethod of claim 9 wherein the powder is sprayed onto the article. 11.The method of claim 10 wherein the powder has a charge applied thereto.12. The method of claim 1 wherein the coating material comprises a firstcoating material and a second coating material and wherein the firstcoating material is fully cured to form a first cured layer and thesecond coating material is applied onto the first cured layer.
 13. Themethod of claim 12 wherein the second coating material is a thermosetmaterial.
 14. The method of claim 13 wherein the first coating materialis a fast curing material and the second coating material cures at aslower rate than the first coating material.
 15. The method of claim 12wherein the second coating material is a lubricant.
 16. The method ofclaim 15 wherein the lubricant is one or more of a polyethylene wax, aparaffin wax, a carnauba wax, and a solid lubricant.
 17. The method ofclaim 16 wherein the solid lubricant is one or more of molybdenumdisulfide and a fluoropolymer.
 18. The method of claim 1 wherein thecoating material, when cured, has a substantially uniform thickness ofabout 0.005 to 0.0035 inches.
 19. The method of claim 18 wherein thethickness is about 0.0015 inches.
 20. The method of claim 1 wherein thefirst coating material is an oxide-based ceramic material.
 21. Themethod of claim 1 wherein the curing is heat curing.
 22. The method ofclaim 21 wherein the heat curing is induction heat curing and includesthe application of a magnetic field.
 23. The method of claim 1 whereinthe article to which the first coating material is applied is preheatedprior to application of the first coating material.
 24. The method ofclaim 1 wherein the first and second articles are dissimilar metals. 25.The method of claim 1 wherein one of the first and second articles is anon-metal.
 26. The method of claim 24 wherein when the cured coatingmaterial is present on at least a head of a steel bolt mounted to amagnesium coupon, the magnesium coupon exhibits less than about 3% ofpitting compared to an uncoated steel bolt on the magnesium coupon aftera 15 year simulated test under test procedure GMW17026.
 27. The methodof claim 1 wherein the first article has an anodic index that is greaterthan the second article.
 28. The method of claim 1 wherein the firstarticle comprises iron or an iron alloy.
 29. The method of claim 1wherein the second article comprises magnesium or a magnesium alloy. 30.The method of claim 1 wherein the second article comprises aluminum oran aluminum alloy.
 31. The method of claim 1 wherein the first articleis a male-part fastener.
 32. The method of claim 31 wherein themale-part fastener is a bolt or screw.
 33. The method of claim 31wherein the bolt exhibits a tension loss of no more than about 25% whenheated to a temperature of 125° C. for a period of 800 hours.
 34. Atwo-article system in which first and second articles of the two-articlesystem have surfaces facing one another and in which the two articleshave different anodic indices, the surface of the first articlecomprising a coating layer formed by curing a coating material on thesurface of the first article, and the surface of the first article incontact and secured with the surface of the second article, wherein thetwo articles exhibit substantially no corrosion following exposure to acorrosive environment under standard GMW17026 after a 15 year simulatedtest.
 35. The system of claim 34 wherein the coating material is athermoset material.
 36. The system of claim 35 wherein the thermosetmaterial is a cross-linked epoxy coating.
 37. The system of claim 36wherein the epoxy material is a fusion bond epoxy material.
 38. Thesystem of claim 36 wherein the epoxy material comprises a curing agent.39. The system of claim 38 wherein the curing agent comprises one ormore of more amines, anhydrides, acids, phenols, alcohols and thiols.40. The system of claim 36 wherein the epoxy material comprises one ormore of a filler and a pigment.
 41. The system of claim 36 wherein theepoxy material cures in approximately thirty seconds or less whensubjected to a temperature of about 400 to 450 degrees Fahrenheit toform the cross-linked epoxy coating.
 42. The system of claim 1 whereinthe coating material comprises a first coating material and a secondcoating material, and wherein the first coating material is fully curedto form a first cured layer, and the second coating material is appliedonto the first cured layer to form the coating material.
 43. The systemof claim 42 wherein the second coating material is a thermoset material.44. The system of claim 43 wherein the first coating material is a fastcuring material and the second coating material cures at a slower ratethan the first coating material.
 45. The system of claim 42 wherein thesecond coating material is a lubricant.
 46. The system of claim 45wherein the lubricant is one or more of a polyethylene wax, a paraffinwax, a carnauba wax, and a solid lubricant.
 47. The system of claim 46wherein the solid lubricant is one or more of molybdenum disulfide and afluoropolymer.
 48. The system of claim 34 wherein the coating material,when cured, has a substantially uniform thickness of about 0.005 to0.035 inches.
 49. The system of claim 48 wherein the thickness is about0.001 to 0.0025 inches.
 50. The system of claim 34 wherein the surfaceof the first article comprises an oxide-based ceramic material to whichthe coating material is applied.
 51. The system of claim 34 wherein thefirst and second articles are dissimilar metals.
 52. The system of claim34 wherein one of the first and second articles is a non-metal.
 53. Thesystem of claim 34 wherein the first article is a steel bolt and thesecond article is formed from a metal having a lesser anodic index. 54.The system of claim 53 wherein the second article is formed frommagnesium and wherein the cured coating material is present on at leasta head of the steel bolt, and wherein when mounted to a magnesiumcoupon, the magnesium coupon exhibits less than about 3% of pitting of acomparable uncoated steel bolt on the magnesium coupon after a 15 yearsimulated test under test procedure GMW17026.
 55. The system of claim 34wherein the first article has an anodic index that is greater than thesecond article.
 56. The system of claim 34 wherein the first articlecomprises iron or an iron alloy.
 57. The system of claim 34 wherein thesecond article comprises magnesium or a magnesium alloy.
 58. The systemof claim 34 wherein the second article comprises aluminum or an aluminumalloy.
 59. The system of claim 34 wherein the first article is amale-part fastener.
 60. The system of claim 59 wherein the male-partfastener is a bolt or screw.
 61. The system of claim 59 wherein thescrew exhibits a tension loss of no more than about 25% when heated to atemperature of 125° C. for a period of 800 hours.
 62. The system ofclaim 34 wherein the first article is a steel bolt and wherein thecoating layer is present on at least a head and an underside of the headof the steel bolt.